Fe/Mn-Synergistic Promoted C(sp³)–BiCross-Coupling of Alkyl Chlorides with Chlorobismuthanes to AccessAir-Stable Alkylbismuthanes

Alkylating bismuthanes containing C(sp³)–Bi bonds were first disclosed as early as 1850, but their development remains severely limited, especially the synthetic method. Herein, we developed the first Fe/Mn-synergistic promoted C(sp³)–Bi cross-coupling of alkyl halides with chlorobismuthanes, which can access alkylbismuthanes in satisfactory yields with various functional group compatibility (cyano, ester, aldehyde, and amide). Inactivated alkyl chlorides/bromides, as well as cyclic and acyclic alkyl electrophiles, smoothly yielded the corresponding products. Gram-scale synthesis and late-stage modification of drug molecules were also conducted. The synthesized alkylbismuthanes also could be alkylation reagents toward C(sp³)–C(sp²), C(sp³)–Se, C(sp³)–S, and C(sp³)–N bonds.